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As quantum computing, communication, and sensing play increasingly important roles in the coming decades, and the demands for high sensitivity imaging grow rapidly, the sensitivity of photodetectors has become a main concern in several key technology sectors. This thesis reports two novel light detection and internal amplification mechanisms that enable photodiodes to achieve desired characteristics such as high detection efficiency, single photon sensitivity, low noise and high speed. Cycling excitation process (CEP) is an intrinsic signal amplification mechanism that was firstly discovered in a heavily-doped compensated Si p/n junction device. By relaxing the k-selection rule (i.e. conservation of momentum), CEP detectors possess high gain, high efficiency, and ultralow noise. Above all, CEP detectors can be made from disordered materials such as amorphous silicon (a-Si), which allows low cost manufacturing and scalability to large array size for intended applications. An a-Si photodiode is demonstrated with ultra-high gain-bandwidth product of 2.25 THz and low noise, based on a very simple structure. Dark current is a key challenge for photodiodes to detect extremely low power such as single photon as it can produce shot noise. A proper designed based on band gap engineering is shown to reduce the dark current of a-Si CEP detectors. The result of temperature dependent dark current measurement conveys the message that the dark current mechanism of a-Si CEP detectors is indirect tunneling followed by Poole-Frenkel effect. The key part is how to block the electron tunneling without affecting the device photo response. Cupric oxide (Cu2O) is an intrinsic p-type semiconductor material, with electron affinity of -3.2 eV and band gap of 2.1 eV. By inserting a thin layer of Cu2O between the a-Si and top electrode, the new structure has a much large electron tunneling barrier. On the other hand, the photogenerated holes can move as before without any additional hole blocking barrier. The measured results support that Cu2O based dark current reduction CEP devices have at least 1-2 orders of magnitude lower dark current at reverse bias 5 V compared to the typical a-Si CEP detectors while the photo responsivity remain the same.Realizing that CEP effect occurs in a thin layer of a-Si, we designed an a-Si CEP detector without any semiconductor substrate. The key challenges are to improve the absorption efficiency and frequency response. Utilizing the localized surface plasmon resonance (LSPR) effect incorporated with CEP effect, a plasmonically enhanced a-Si detector achieves high external quantum efficiency with a record fast impulse response of 170 ps (FWHM). This approach raises the possibility of making detectors out of amorphous materials for high frame rate imaging and optical communications in spite of the low carrier mobilities in the materials.The second optical signal amplification mechanism was observed in organometallic perovskite based detectors when the input power was down to a few or even single photon. It is a quasi-persistent photo response which takes tens of seconds for the current level to increase and reach to saturation after the absorption of a single photon. Based on the observation, we proposed an internal amplification mechanism, ionic impact ionization (I3), to elucidate the phenomenon, which involves a cascade process of ion migration.

By placing a single Au nanoparticle on the surface of a cadmium sulfide (CdS) nanowire, we demonstrate strong coupling of localized surface plasmon resonance (LSPR) modes in the nanoparticle and whispering gallery modes (WGMs) in the nanowire. For a 50-nm-diameter Au-nanosphere particle, strong coupling occurs when the nanowire diameter is between 300 and 600 nm, with a mode splitting up to 80 meV. Using a temperature-induced spectral shift of the resonance wavelength, we also observe the anticrossing behavior in the strongly coupled system. In addition, since the Au nanosphere has spherical symmetry, the supported LSPR mode can be selectively coupled with transverse electric (TE) and transverse magnetic (TM) WGMs in the nanowire. The ultracompact strong-coupling system shown here may provide a versatile platform for studying hybrid “photon–plasmon” nanolasers, nonlinear optical devices, and nanosensors.

When plasmonic nanoparticles (PNPs) are illuminated by a light source with a plasmon frequency, an intensive localized surface plasmon resonance (LSPR) effect can be excited, which causes an obvious enhancement of the local electric field around the PNPs. The light energy is converted into heat by the PNPs, causing a gradual increase in the temperature of the media around these PNPs. Under the induction of radiation, the heat generated by PNPs vaporizes the surrounding water, and under the combined effect of the local electric field, plasmonic nanobubbles (PNBs) are generated. After that, PNBs will continue to grow, which is mainly caused by the influx of dissolved gas from the surrounding water. With the growth of PNBs, PNB-induced micro convection and some unique nonlinear changes of optical properties can be observed. Since the size, location and lifetime of PNBs can be flexibly controlled by adjusting the parameters of the light source, PNBs have been widely used in several emerging applications such as microfluidic manipulations, medical drug delivery and cell therapy. In this review, we first introduce the physical mechanism of PNB generation and discuss the micro convection and optical nonlinearity caused by PNBs. In addition, we demonstrate the nucleation mechanism and the growth kinetics of PNBs. Then we review the PNBs-based applications in microfluid flow control, particle manipulation, optical property tuning, medical drug delivery and cancer therapy. Finally, we summarize the current challenges of this field and propose an outlook for future developments.

Gold nanoparticle ensembles were prepared by laser dewetting from a gold thin film on a glass substrate. The gold film was scanned by infrared laser (1064 nm) using a fiber laser scanner. The morphology, color, and shading of the nanoparticles were controlled by changing two parameters, the laser intensity and the laser scan rate. Laser printing of a multicolor image was successfully demonstrated. This simple method would be applied to patterning of electrodes and semiconductor films with gold nanoparticle ensembles with different optical properties.

Optical nanomaterials have attracted tremendous interest from a large community of researchers because of their widespread applications. The optical properties are closely related the structures of nanomaterials, thus making the structural engineering over nanomaterials in a controlled manner an important topic. This dissertation discusses our efforts in the engineering and applications of optical nanomaterials including noble metal nanostructures and hollow nanostructures.Noble metal nanostructures possess novel optical properties due to localized surface plasmon resonances. Controllable synthesis of noble metal nanostructures with desired morphology and optical properties is highly desirable. In this work, we attempt to prepare anisotropic Ag/Au alloy nanorods with homogenous compositions through a high-temperature annealing process. Alloy nanorods exhibit strong surface plasmon resonances with high stability upon etching. Tunable and fascinating optical properties are achieved through controlling over aspect ratios and compositions of the nanorods.Improved understandings on the properties of resorcinol-formaldehyde (RF) resins will benefit the colloidal synthesis of RF-based nanomaterials. In this study, the chemical stability and the evolution of both surface properties and chemical structures of RF resin spheres are systematically studied, which provide guidance for the rational design and fabrication of various hollow nanostructures. Based on the new understandings, an extension of the surface-protected etching strategy has been adopted for the preparation and engineering of hollow RF nanostructures. A RF-template-engaged redox reaction method is proposed and utilized for rational synthesis of mesoporous hollow manganese oxide nanostructures. Visible resonant Mie scattering properties are theoretically simulated and experimentally demonstrated.Finally, a couple of novel optical demonstrations based on the design and structural engineering of nanostructures are presented. The first one is the design of plasmonic dichroic film on a mirrored substrate, which has been realized by spray-coating core-shell nanostructures. By structural engineering over the core-shell particles, dichroic film with multi-colors has been successfully created, which holds great potential in anti-counterfeiting. The other one is related to the modulation of light transmittance and the drying process of hollow nanostructures. Au nanoparticles are incorporated into the hollow structures and employed to probe the drying process.

Control of light transmittance is important for optoelectronic devices such as smart windows and switchable photodetectors. In particular, that for infrared light can be used for tuning thermal flows through windows. Plasmonic compound nanomaterials are suitable for those devices because of their electrochemically tunable localized surface plasmon resonance (LSPR). We combined CuS nanoplates with MoO3 nanosheets for developing complementary near infrared electrochromic cell. CuS loses its plasmonic absorption (peaked at ∼1100 nm) when it is reduced, as opposed to MoO3, whose absorption at >600 nm is suppressed when it is oxidized. An assembled smart window with rocking-chair type lithium ion transport exhibits wide transmittance changes in the near infrared region.

A composite film composed of Ag nanoparticles, Al2O3 and TiO2 was prepared by cosputtering. Ag NPs were immersed in the Al2O3 host, TiO2 was deposited onto the Ag/Al2O3 layer. The degradation of aqueous methylene blue under incident irradiation indicated that the Ag/Al2O3-TiO2 composite film with the Ag-TiO2 distance of 2nm or 5nm exhibited high degradation rate. Spectral absorptivity and radiant absorption distribution were analyzed through FDTD simulation to analyze the relationship between radiant absorption and photocatalytic activity. Results indicated that the spectrum and distribution of the radiant absorption in the composite film could be rationally regulated to improve photocatalytic activity.

Tuning the plasmonic resonance peak to the deep ultraviolet (DUV) band is critical for plasmonic-enhanced AlGaN-based DUV photodetector. However,the high refractive index of AlGaN layer seriously limits the plasmonic resonance peak in DUV band. Therefore, in this work, we study how various Al nanoparticles on the AlGaN layer surface affect the plasmonic resonance performance. Compared with the Al-based nanosphere, nanohemisphere and nanodisk, the Al-based nanorod is the most suitable candidate for AlGaN-based DUV photodetectors. This is because the DUV plasmonic dipolar mode excited from the upper part of nanorod is not affected by the interface between the nanorods and the AlGaN layer. However, the interface also leads to another plasmonic dipolar mode at longer wavelengths. Moreover, the DUV plasmonic resonance peak will be influenced by the diameter, the height and the Al2O3 layer thickness. We also find that the diffraction can enhance the resonance peak intensity when the Al nanorod period is smaller than the resonance peak wavelength. Besides, to make the enhanced electric field located in active layer, a layer of Ga2O3 shell is proposed to cover Al nanorods, which causes a quadrupole mode in DUV band excited from the sidewall of Al nanorods.

The ascorbic acid (AA) is a biomarker that can be used to detect the symptoms of severe disorders such as scurvy, Parkinson’s, Alzheimer’s, and cardiovascular diseases. In this work, a simple and effective sensor model is developed to diagnose the presence of AA samples. To develop the sensor, a tapered single-mode optical fiber has been used with the well-known phenomenon of localized surface plasmon resonance (LSPR). For LSPR, the tapered region is immobilized with synthesized gold nanoparticles (AuNPs) and zinc oxide nanoparticles (ZnO-NPs) whose absorbance peak wavelengths appear at 519nm and 370nm, respectively. On the basis of nanoparticles (NPs) configurations, two different biosensor probes are developed. In the first one, the sensing region is immobilized with AuNPs and named Probe I. In the second probe, the immobilized layer of AuNPs is further coated with a layer of ZnO-NPs, and a resultant probe is termed as Probe II. The characterizations of synthesized AuNPs and developed fiber probes are done by the ultraviolet-visible (UV-vis) spectrophotometer, high-resolution transmission electron microscope (HR-TEM), atomic force microscopy (AFM), and scanning electron microscope (SEM). To enhance the selectivity, a sensing region of probes is functionalized with ascorbate oxidase enzyme that oxidizes the AA in the presence of oxygen. The response of developed sensor probes is authenticated by sensing the samples of AA in the range from 500 nM to 1 mM, which covers the range of AA found in human bodies, i.e., 40µM–120µM. The performance analysis of the developed sensor probes has been done in terms of their stability, reproducibility, reusability, and selectivity. To observe the stability of AA, a pH-test has also been done that results in a better solubility of AA molecules in phosphate-buffered saline (PBS) solution.

Plasmon-induced carrier transfer at metallic nanoparticle/semiconductor heterojunctions has received great attention because of its tremendous potential in applications, such as photocatalysis and photoelectric and energy conversion. The interfacial structure of the heterojunction is known to play an important role in charge transfer as well as the subsequent chemical reactions. Here, we studied the Au nanoparticle (Au-NP)-loaded (100)-, (110)-, and (111)-oriented single-crystalline strontium titanate (STO) as a model to investigate the effects of interfacial structure on the plasmon-induced charge separation between the metallic nanoparticles and semiconductors. Via photoelectrochemical characterizations, we found that the efficiency of the plasmon-induced water oxidation reaction on STO(100) is more than 1.4 times higher than that on the other two orientation facets. This enhancement was demonstrated to stem from the high oxidation ability of plasmon-induced holes captured in the surface states. Furthermore, the molecular processes of water oxidation were investigated by monitoring the surface oxidation status of Au-NP/STO as intermediates of plasmon-induced water oxidation using in situ electrochemical surface-enhanced Raman spectroscopy. The onset potential of Au-O vibrations on Au-NP/STO(100) was determined to be 0.4 V more negative than that of Au-NP/STO(110), further confirming the higher oxidation ability of the plasmon-induced holes. Our observation provides an opportunity to efficiently modulate plasmon-excited hot-carrier reaction processes for photochemical applications through interfacial engineering.

Supercapacitors with high power density, ultralong lifespan and wide range operating temperature have drawn significant attention in recent years. However, monitoring the state of charge in supercapacitors in a cost-effective and flexible way is still challenging. Techniques such as transmission electron microscopy and X-ray diffraction can analyze the characteristics of supercapacitor well. But with large size and high price, they are not suitable for daily monitoring of the supercapacitors’ operation. In this paper, a low cost and easily fabricated fiber-optic localized surface plasmon resonance (LSPR) probe is proposed to monitor the state of charge of the electrode in a supercapacitor. The Au nanoparticles were loading on the fiber core as LSPR sensing region. In order to implant the fiber in the supercapacitor, a reflective type of fiber sensor was used. The results show that this tiny fiber-optic LSPR sensor can provide online monitoring of the state of charge during the charging and discharging process in situ. The intensity shift in LSPR sensor has a good linear relationship with the state of charge calculated by standard galvanostatic charging and discharging test. In addition, this LSPR sensor is insensitive to the temperature change, presenting a great potential in practical applications.

We investigated the temperature-dependent optical response of ordered lattices of noninteracting gold-core/poly(N-isopropylacrylamide)-shell nanoparticles (NPs), a system with proven photothermal a...

Based on localized surface plasmon resonance (LSPR) enhanced quantum dot (QD) emission in a sandwich assay of “capture PCT antibody/PCT/detection PCT antibody labelled with QD” on a gold nanoarray chip, a fully automated point-of-care (POC) system for quick quantitative analysis of procalcitonin (PCT) for sepsis diagnostics was developed. The core technology of the system is to design and fabricate gold nanostructures that can generate plasmonics at resonant wavelength coincident with excitation wavelength of the fluorescent dyes. Gold nanopillar arrays at the size of 140 nm square and 320 nm pitch were found to be good candidates for the desired dye emission. Gold nanochip fabricated by e-beam lithography or nanoimprinting was integrated into a microfluidic chip, with analyte sampling and bioassay reagent flow controlled by LabVIEW program. To detect QD emission of the bioassay from the chip, a CCD camera and a laser source controlled by LabVIEW were incorporated to form a user-friendly and fully-automated POC system for on-site detection of PCT in clinics. Upon detection, the microfluidic chip is inserted into the POC system, where the processes of blood sample loading, detection antibody recognition, fluorescent dye labelling, fluorescent detection, and data analysis are conducted automatically in the device within 30 min at a test sensitivity of 0.5 ng/ml, which fulfills the clinical needs for diagnosis of sepsis through PCT biomarker.

Photoacoustic imaging (PAI) combines the advantage of optical and ultrasonic imaging, which has a high signal-to-noise ratio, and spatial resolution. To further improve the performance of PAI, gold nanorods can be utilized as exogenous contrast agents, and their size can be controlled. The size change of gold nanorods will change their absorption and heat transfer characteristics, and then affect their photoacoustic characteristics. Therefore, in the present work, the influences of absorption characteristics (absorption cross section and volume absorption coefficient) and heat transfer characteristics (specific surface area) of gold nanorods on photoacoustic response are studied by FDTD (FDTD Solutions, Lumerical) and FEM (Comsol Multiphysics). Results show that the increase of specific surface area will enhance the thermal coupling between gold nanorods and water, so as to improve the heat transfer and produce different photothermal responses without significantly affecting the photoacoustic quantum yield (As the specific surface area increases by about 10 times, the temperature increases by about 12 times, while the photoacoustic quantum yield increases by about 24%). On the contrary, absorption characteristics are decisive factors for both photothermal and photoacoustic responses. Therefore, in terms of improving photoacoustic quantum yield, when the size of gold nanorods changes, more attention should be paid to the improvement of the absorption characteristics rather than the specific surface area. In addition, increasing the specific surface area can significantly improve the photostability of gold nanorods, which is very important for practical applications.

Nanocluster aggregation sources based on magnetron-sputtering represent precise and versatile means to deposit a controlled quantity of metal nanoparticles at selected interfaces. In this work, we exploit this methodology to produce Ag/MgO nanoparticles (NPs) and deposit them on a glass/FTO/TiO2 substrate, which constitutes the mesoscopic front electrode of a monolithic perovskite-based solar cell (PSC). Herein, the Ag NP growth through magnetron sputtering and gas aggregation, subsequently covered with MgO ultrathin layers, is fully characterized in terms of structural and morphological properties while thermal stability and endurance against air-induced oxidation are demonstrated in accordance with PSC manufacturing processes. Finally, once the NP coverage is optimized, the Ag/MgO engineered PSCs demonstrate an overall increase of 5% in terms of device power conversion efficiencies (up to 17.8%).

In this study, a novel label-free immunosensor platform is developed to exploit the localized surface plasmon resonance (LSPR) phenomenon. The LSPR solution-based platform is designed by a gold nanospheres probe, functionalized with monoclonal anti-dengue antibody (IgG). Numerical calculations are performed to assess the LSPR extinction spectrum and spatial near electric field distribution around the nanoparticle surface. Important parameters that govern sensor performance, molecular and refractive index sensitivity are evaluated. On the evaluation of the platform as a molecular sensor, the detection of dengue NS1 antigens is presented. The results are consistent with the numerical simulations, which depicts the system’s ability to identify dengue NS1 antigen concentrations as low as 0.07 ± 0.01 µg/mL, along with fosters its potential application in plasmonic sensing.

Pressure-sensitive films have been used for measurement in micro flow, but thin films have very limited intensity, resulting in poor signal-noise ratio (SNR). This paper presents a pressure-sensitive film whose emission signal is enhanced by silver nanoparticles (AgNPs) based on localized surface plasmon resonance (LSPR). Electronic beam evaporator and annealing furnace are used to fabricate silver nanotexture surface. PtTFPP and polystyrene are dissolved in toluene and then spin-coated on the silver nanotexture surface to prepare the pressure-sensitive films. Signal enhancement of film with AgNPs due to LSPR is analyzed and enhancement effect of samples with different particle sizes and spacer thickness are compared. Pressure and temperature calibrations are performed to assess the sensing performance of pressure-sensitive films. Pressure-sensitive films with AgNPs demonstrate signal enhancement due to LSPR and show promise for measurement in micro flow.

A tunable infrared optical switch based on a plasmonic structure consisting of aluminum nanoarrays with a thin film of vanadium dioxide is proposed. This optical switch can realize arbitrary wavelength-selective optical switching in the mid-infrared region by altering the radii of the aluminum nanoarrays. Furthermore, since vanadium dioxide transforms from its low-temperature insulator phase to a high-temperature metallic phase when heated or applied voltage, the optical switch can achieve two-way switching of its “ON” and “OFF” modes. Finite-difference time-domain software is used to simulate the performance of the proposed infrared optical switch. Simulation results show that the switch offers excellent optical performances, that the modulation depth can reach up to 99.4%, and that the extinction ratio exceeds −22.16 dB. In addition, the phase transition time of vanadium dioxide is on the femtosecond scale, which means that this optical switch based on a vanadium dioxide thin film can be used for ultrafast switching.

Plasmonic nanofluids have excellent optical properties in solar energy absorption and have been widely studied in solar thermal conversion technology. The absorption of the visible region of solar energy by ordinary metal nanoparticles is usually limited to a narrow resonance band, so it is necessary to enhance the coupling effect of nanoparticles in the visible spectrum region to improve absorption efficiency. However, it is still a difficult task to improve solar energy absorption by adjusting the structure and performance of nanoparticles. In this paper, a plasma dimer Ag nanoparticle is proposed to excite localized surface plasmon resonance (LSPR). Compared with an ordinary Ag nanoparticle in the visible region, the plasmonic Ag dimer nanoparticle produces more absorption peaks and broader absorption bands, which can broaden solar energy absorption. By analyzing the electromagnetic field of the nanoparticle, the resonance mode of the plasma dimer is discussed. The effects of the geometric dimensions of the nanoparticle and the embedding of two spheres on the optical properties are studied. In addition, the effects of a trimer and its special structure on the optical properties are also analyzed. The results show that the proposed plasma dimer Ag nanoparticle has broad prospects for application in solar thermal conversion technology.

The electron density of a nanoparticle is a very important characteristic of the properties of a material. This paper describes the formation of silver nanoparticles (NPs) and the variation in the electronic state of an NP’s surface upon the reduction in Ag+ ions with oxalate ions, induced by UV irradiation. The calculations were based on optical spectrophotometry data. The NPs were characterized using Transmission electron microscopy and Dynamic light scattering. As ~10 nm nanoparticles are formed, the localized surface plasmon resonance (LSPR) band increases in intensity, decreases in width, and shifts to the UV region from 402 to 383 nm. The interband transitions (IBT) band (≤250 nm) increases in intensity, with the band shape and position remaining unchanged. The change in the shape and position of the LSPR band of silver nanoparticles in the course of their formation is attributable to an increasing concentration of free electrons in the particles as a result of a reduction in Ag+ ions on the surface and electron injection by CO2− radicals. The ζ-potential of colloids increases with an increase in electron density in silver nuclei. A quantitative relationship between this shift and electron density on the surface was derived on the basis of the Mie–Drude theory. The observed blue shift (19 nm) corresponds to an approximately 10% increase in the concentration of electrons in silver nanoparticles.

The optical near field (NF) induced by circularly polarized light (CPL) is a hot scientific topic. We observed a chiral NF intensity distribution on a series of achiral gold nanorectangular structures (Au-NRs) under CPL irradiation by using multiphoton photoemission electron microscopy (MP-PEEM). Additionally, the differential NF spectra under left and right CPL irradiation, which represent the asymmetry of the NF intensity distribution, were investigated. We propose an interpretation that the chiral NF intensity distribution on an achiral metallic nanostructure is extrinsically generated by the interference between two plasmonic modes by combining state-of-the-art MP-PEEM techniques and the classical oscillator model. Our interpretation well explains both the experimental and simulation results. Furthermore, the intensity of the NF and its phase angle of each mode under linearly polarized light irradiation were revealed to be critical factors for the generation of extrinsic chirality in the NF intensity distribution.

Function expansion of fiber sensor is highly desired for ultrasensitive optical detection and analysis. Here, we present an approach of multifunctional fiber sensor based on Fano resonances and localized surface plasmon resonance (LSPR) excited via cylindrical vector beam with ability of refractive index (RI) sensing, nano-distance detection, and surface enhanced Raman spectroscopy (SERS). Silver (Ag)-nanocube modified microfiber is theoretically proved to enable to detect RI of the nearby solids and gases based on Fano resonances with a sensitivity of 128.63 nm/refractive index unit (RIU) and 148.21 nm/RIU for solids and gases, respectively. The scattering spectrum of the Ag nanocube has the red-shift response to the varies of the nano-distance between the nanocube and the nearby solid, providing a detection sensitivity up to 1.48 nm (wavelength)/nm (distance). Moreover, this configuration is theoretically verified to have ability to significantly enhance electric field intensity. Radially polarized beam is proved to enhance the electric field intensity as large as 5 times in the side-face configuration compared with linear polarization beam. This fiber-based sensing method is helpful in fields of remote detection, multiple species detection, and cylindrical vector beam-based detection.

Nanocrystals (NCs) of transparent conducting oxides with a localized surface plasmon resonance (LSPR) in the near-infrared (NIR) spectral region show promising electrochromic properties for the development of a new generation of dynamic "smart windows". In this regard, we exploit thin films of F, In-codoped CdO (FICO) NCs as active coatings for electrochromic devices. The control over the dopants concentration in FICO NCs results in fine tuning of their LSPR across the NIR region of the electromagnetic spectrum. Highly transparent mesoporous electrodes were prepared from colloidal FICO NCs by in situ ligand exchange of the pristine organic capping ligands. This approach preserves the optical and electrical properties of native NCs and delivers highly homogeneous, nonscattering films with a good electronic coupling between the NCs. We achieved a dynamic control over the LSPR frequency by reversible electrochemical doping, hence a spectrally selective modulation of the optical transmittance in the NIR region of the solar spectrum, which carries nearly 50% of the whole solar heat. Spectroelectrochemical characterization, coloration efficiency, and switching kinetics results indicate that thin film based on FICO NCs are potential candidates for plasmonic electrochromic applications. Moreover, the high electron mobility and wide optical bandgap of FICO makes NCs of this material suitable for large-area devices capable of dynamically controlling the heat load coming from the solar infrared radiation, without affecting the visible light transmittance.

"Available online 09 March 2019", This work reports on the development of a label-free immunosensor technology, based on nanoplasmonic Au-TiO2 thin films. The Au-TiO2 thin films were prepared by cost-effective reactive DC magnetron sputtering, followed by a thermal annealing procedure. The latter promoted the growth of the Au nanoparticles throughout the TiO2 matrix and induced some morphological changes, which are the base for the immunosensor device functionality. A posterior plasma etching treatment was required to partially expose the nanoparticles to the biological environment. It gave rise to a 6-fold increase of the total area of gold exposed, allowing further possibilities for the sensor sensitivity enhancement. Experimental results demonstrated the successful functionalization of the films' surface with antibodies, with the immobilization occurring preferentially in the exposed nanoparticles and negligibly on the TiO2 matrix. Antibody adsorption surface coverage studies revealed antibody low affinity to the film's surface. Nevertheless, immunoassay development experiments showed a strong and active immobilized antibody monolayer at an optimized antibody concentration. This allowed a 236 signal-to-noise-ratio in a confocal microscope, using mouse IgG and 100 ng/ml of Fab-specific anti-mouse IgG-FITC conjugated. Label-free detection of the optimized antibody monolayer on Au-TiO2 thin films was also tested, revealing an expected redshift in the LSPR band, which demonstrates the suitability for the development of cost-effective, label-free LSPR based immunosensor devices., Authors would like to acknowledge FROnTHERA (NORTE-01-0145-FEDER-0000232), VM Correlo acknowledges Investigator FCT program(IF/01214/2014). Coauthors from CFUM acknowledge FCT in the fra-mework of the Strategic Funding UID/FIS/04650/2013; project POCI-01-0145-FEDER-016902, with FCT reference PTDC/FIS-NAN/1154/2014; and project POCI-01-0145-FEDER-032299, with FCT referencePTDC/FIS-MAC/32299/2017. Joel Borges also acknowledges FCT forhis Post-Doc Grant SFRH/BPD/117010/2016 and Marco S. Rodriguesacknowledges his PhD-Grant from FCT, with reference SFRH/BD/118684/2016., info:eu-repo/semantics/publishedVersion

In this study, plasmonic nanostructures were examined to enhance the light harvesting of organic thin-film solar cells (OSCs) by multiple surface plasmon resonance (SPR) phenomena originating from the grating-coupled configuration with a Blu-ray Disc recordable (BD-R)-imprinted aluminum (Al) grating structure and the incorporation of a series of silver nanodisks (Ag NDs). The devices with such a configuration maximize the light utilization inside OSCs via light absorption, light scattering, and trapping via multiple surface plasmon resonances. Different types and sizes of metallic nanoparticles (NPs), i.e., gold nanoparticles (Au NPs), Ag nanospheres (Ag NSs), and Ag NDs, were used, which were blended separately in a PEDOT:PSS hole transport layer (HTL). The device structure comprised of grating-imprinted-Al/P3HT:PCBM/Ag ND:PEDOT:PSS/ITO. Results obtained from the J–V curves revealed that the power conversion efficiency (PCE) of grating-structured Al/P3HT:PCBM/PEDOT:PSS/ITO is 3.16%; this value is ~6% higher than that of a flat substrate. On the other hand, devices with flat Al and incorporated Au NPs, Ag NSs, or Ag NDs in the HTL exhibited PCEs ranging from 3.15% to 3.37%. Furthermore, OSCs with an Al grating substrate were developed by the incorporation of the Ag ND series into the PEDOT:PSS layer. Compared with that of a reference device, the PCEs of the devices increased to 3.32%–3.59% (11%–20% improvement), indicating that the light absorption enhancement at the active layer corresponds to the grating-coupled surface plasmon resonance and localized surface plasmon resonance excitations with strong near-field distributions penetrating into the active layer leading to higher efficiencies and subsequent better current generation.

We propose a novel localized surface plasmon resonance (LSPR) sensor system based on polymer material. The proposed LSPR system consists of the incident medium with low-loss polymer waveguide and the chemically immobilized plasmonic nanoparticles for on-chip LSPR sensing. Because of low coupling efficiency of conventional methods, usually intricate test equipment such as dark field microscopes equipped with cooled charge-coupled device detectors is required to perform nanoparticles LSPR sensing. Using a polymer optical waveguide instead of conventional free-space excitation techniques (e.g., using an objective lens) in the LSPR sensing system offers miniaturization, low cost, and potable sensing capability. The integration of this hybrid plasmonic-photonic sensor with optical system based on fiber optic is measured to refractive index with a sensitivity of 3.10/RIU.

One of prospective ways for boosting efficiency of luminescent materials is their combination with noble metal nanoparticles. Collective, so-called plasmon, oscillations of surface electrons in a nanoparticle can resonantly interact with incident or fluorescent light and cause an increase in the light absorption cross section or radiative rate for an adjacent emitter. Plasmonic inorganic phosphors require gentle host crystallization at which added noble nanoparticles will not suffer from aggregation or oxidation. The prospective plasmonic Mg2TiO4:Mn4+ phosphor containing core@shell Ag@SiO2 nanoparticles is prepared here by spare low-temperature annealing of a sol-gel host precursor. It is revealed that Mn4+ luminescence nonmonotonously depends on the size and concentration of 40 and 70 nm silver nanoparticles. It is demonstrated that luminescence of the Mg2TiO4:Mn4+ phosphor can be up to a 1.5 times increase when Mn4+ excitation is supported by localized surface plasmon resonance in Ag@SiO2 nanoparticles. © 2019 American Chemical Society.

Infrared spectroscopy is an effective technique extensively used in research and industry for the label-free and unambiguous identification of molecular species. However, the sensitivity of this technique is severely limited as a result of Beer's law and, the small infrared absorption cross-section that make prohibitively weak the absorption signals, of minute amounts of analyte as those present in monolayers. This limitation can be overcome by enhancing the infrared vibration of molecules through the enhancement of the electromagnetic (EM) field. Surface Enhanced InfraRed Absorption (SEIRA) using resonant metal Nano-scale Antennas (NAs) can provide huge electromagnetic fields on the nanometer scale featuring localized collective oscillations of electrons, an effect named Localized Surface Plasmonic Resonances (LSPRsWe here report on a series of 2D arrays of cross-shaped NAs having several mm(2) area coverage (metasurface) as SEIRA optimized antennas, which can be used in practical applications such as the vibrational sensing of chemical and biological analytes. Cross-shape designed NAs are insensitive to the polarization of the electromagnetic radiation impinging the active area. Due to the random orientation of the dipole moments of molecules they are particularly suitable for the construction of bio-molecular sensors. At the same time, the 2D-array configuration ensures a good near-field signal enhancement arising from the coupling between neighbour NAs Moreover, SEIRA NAs can be easily integrated with micrometre-sized channels and be suitable for the high sensitivity, real time analysis of IR emitting samples, in matrices where IR spectroscopy is severely limited due to absorption bands of liquid water. We present the design, fabrication and experimental characterization of large-area metasurfaces based on cross-shaped plasmonic NAs for the spectroscopic characterization of various types of compounds and for sensing applications in the mid-infrared range. The cross-shaped NAs we have designed exhibit SEIRA phenomena which are very sensitive to both refractive index changes in the surrounding medium and to the specific molecular vibration band emerging from surface adsorbed molecules. To test this effect on our device, we have used as model compounds small molecules (molecular weight (MW) < 500 g/mol) containing triple bond groups resonating at about 2100 cm(-1) and a large polymer (MW (similar to) 950,000 g/mol) containing carbonyl groups resonating at wavenumbers of about 1700 cm-1. We show a sensitivity of 600 nm/RIU at different wavelengths at a maximum amount of immobilized small molecule of 0.7 fmoles and a SEIRA enhancement factor of 48,000. We also show the device potential to reveal chemical reactions, occurring on the sensor surface at the same scale, where the nitrile group is converted to a triazole ring.

In this work, thin films composed of gold (Au), silver (Ag), and copper (Cu) metals, dispersed in aluminium nitride (AlN), were prepared by reactive direct current magnetron sputtering, and post-deposition thermal annealing. The structure, morphology and optical response of the films were studied as a function of the composition and annealing temperature. The atomic concentration of the plasmonic metal (Au, Ag and Cu), ranged from 2 to 6 at.% in Au, 4 to 11 at.% in Ag and 3 to 10 at.% in Cu. The formation of Au and Ag nanoparticles dispersed in the AlN matrix was observed only for the Au and Ag systems. The average sizes of the nanoparticles increased with the increase of the annealing temperature, up to 6 nm in the case of Au and 12 nm for the case of the Ag. The Au:AlN system revealed plasmonic response at temperatures of 500 °C and above, with clear localized surface plasmon resonance, LSPR, bands in the visible range (520–540 nm). The Ag:AlN films showed a LSPR band at lower temperatures (300 °C), at wavelengths around 380 nm, shifting to 410 nm at higher annealing temperatures. In some cases, Ag clusters were also formed on the top of the Ag:AlN films, leading to a nearly flat absorption band from visible to infrared wavelengths. In the case of the Cu:AlN thin films, the optical response did not exhibit any characteristics associated to the LSPR effect., This research was sponsored by the Portuguese Foundation for Science and Technology (FCT) in the framework of the Strategic Funding UID/FIS/04650/2013; FCT Project POCI-01-0145-FEDER-016902, with reference PTDC/FIS-NAN/1154/2014; and SAICT – IC&DT FCT project POCI-01-0145-FEDER-032299 with reference PTDC/FIS-MAC/32299/2017. Joel Borges also acknowledges FCT for his Post-Doc Grant SFRH/BPD/117010/2016, Marco S. Rodrigues acknowledges his PhD-Grant from FCT, with reference SFRH/BD/118684/2016 and C. Lopes acknowledges FCT for the PhD-Grant SFRH/BD/103373/2014., info:eu-repo/semantics/publishedVersion

The optical properties of Cu island films, in particular their plasmonic behaviour, are investigated. The films are fabricated by electron beam evaporation using different deposition parameters (deposited mass thickness and substrate temperature). The optical response can be tuned from a metal-like behaviour to well-defined localized surface plasmon resonances and is well correlated with the structural and morphological properties of the samples. Significant changes of optical properties take place with sample aging, including quenching and non-monotonic frequency shift of the plasmon resonance. These changes are interpreted in terms of Cu oxidization process, that appears to strongly depend on the initial morphology of samples. Theoretical calculations in the framework of effective medium theories qualitatively explain the experimental observations. Overall, the results give a detailed insight on the morphology dependence and time evolution of the optical response of Cu island films that may provide useful guidelines for applying these nanostructures in plasmonic applications.

The near-field enhancement and localized surface plasmon resonance (LSPR) on the core-shell noble metal nanostructure surfaces are widely studied for various biomedical applications. However, the study of the optical properties of new plasmonic non-spherical nanostructures is less explored. This numerical study quantifies the optical properties of spherical and non-spherical (prolate and oblate) dimer nanostructures by introducing finite element modelling in COMSOL Multiphysics. The surface plasmon resonance peaks of gold nanostructures should be understood and controlled for use in biological applications such as photothermal therapy and drug delivery. In this study, we find that non-spherical prolate and oblate gold dimers give excellent tunability in a wide range of biological windows. The electromagnetic field enhancement and surface plasmon resonance peak can be tuned by varying the aspect ratio of non-spherical nanostructures, the refractive index of the surrounding medium, shell thickness, and the distance of separation between nanostructures. The absorption spectra exhibit considerably greater dependency on the aspect ratio and refractive index than the shell thickness and separation distance. These results may be essential for applying the spherical and non-spherical nanostructures to various absorption-based applications.

The plasmonic properties of bimetallic (gold and silver) core-shell nanostructures were studied numerically by using the boundary element method implemented in MATLAB (MNPBEM toolbox). The dependence of the bulk refractive index sensitivity of the nanostructures on the core/shell thicknesses was investigated, and regions of enhanced sensitivities were identified for both Ag@Au and Au@Ag type of nanostructures. For Ag@Au nanoparticles, utilizing a 14 ± 2 nm silver core radius with 4 ± 2 nm gold shell thickness or a 22 ± 2 nm core radius with 6 ± 1 nm shell thickness can yield a 1.2–2.5× increase in sensitivity compared to a purely silver nanosphere with the same size. For Au@Ag structures, 20 ± 3 nm gold core size with 10 ± 3 nm silver shell thickness was found to be optimal, with sensitivity enhancements between 2 and 5× compared to pure gold nanoparticles with the same size. The increased sensitivity can always be attributed to the hybridization of the plasmon absorbance peaks corresponding to the silver and gold parts, which merging comes with increased peak width (and thus decreased figure of merit) as a tradeoff. The provided sensitivity maps can be helpful for the design and fabrication of plasmonic sensors utilizing core-shell nanostructures.

A plasmonic sensing platform was developed as a noninvasive method to monitor gas-phase biomarkers related to cystic fibrosis (CF). The nanohole array (NHA) sensing platform is based on localized surface plasmon resonance (LSPR) and offers a rapid data acquisition capability. Among the numerous gas-phase biomarkers that can be used to assess the lung health of CF patients, acetaldehyde was selected for this investigation. Previous research with diverse types of sensing platforms, with materials ranging from metal oxides to 2-D materials, detected gas-phase acetaldehyde with the lowest detection limit at the µmol/mol (parts-per-million (ppm)) level. In contrast, this work presents a plasmonic sensing platform that can approach the nmol/mol (parts-per-billion (ppb)) level, which covers the required concentration range needed to monitor the status of lung infection and find pulmonary exacerbations. During the experimental measurements made by a spectrometer and by a smartphone, the sensing examination was initially performed in a dry air background and then with high relative humidity (RH) as an interferent, which is relevant to exhaled breath. At a room temperature of 23.1 °C, the lowest detection limit for the investigated plasmonic sensing platform under dry air and 72% RH conditions are 250 nmol/mol (ppb) and 1000 nmol/mol (ppb), respectively.

We propose and demonstrate a sensing platform based on plasmonic metasurfaces for the detection of very low concentrations of deoxyribo-nucleic acid (DNA) fragments. The platform relies on surface-enhanced infrared absorption spectroscopy, implemented via a multispectral metasurface. Specifically, different regions (“pixels”) are engineered so as to separately cover the medium-infrared range of the electromagnetic spectrum extending from the functional-groups to the fingerprint region of a single analyte. In conjunction with a suitable bio-functionalization, this enables univocal and label-free recognition of specific molecules. For experimental validation, we fabricate a large-area gold metasurface on a silicon chip, and functionalize it with a recognition layer of peptide nucleic acid (PNA). Our experimental results indicate the possibility to detect complementary DNA fragments in concentrations as low as 50 fM, i.e., well below the value attained by standard methods, with additional advantages in terms of processing time, versatility and ease of implementation/operation.

Localized surface plasmon resonance (LSPR)-based biosensors have recently garnered increasing attention due to their potential to allow label-free, portable, low-cost, and real-time monitoring of diverse analytes. Recent developments in this technology have focused on biochemical markers in clinical and environmental settings coupled with advances in nanostructure technology. Therefore, this review focuses on the recent advances in LSPR-based biosensor technology for the detection of diverse chemicals and biomolecules. Moreover, we also provide recent examples of sensing strategies based on diverse nanostructure platforms, in addition to their advantages and limitations. Finally, this review discusses potential strategies for the development of biosensors with enhanced sensing performance.

The localized surface plasmon resonance of metallic nanoparticles has attracted much attention owing to its unique characteristics, including the enhancement of signals in sensors and photothermal effects. In particular, hollow gold nanostructures are highly promising for practical applications, with significant advantages being found in their material properties and structures: 1) the interaction between the outer surface plasmon mode and inner cavity mode leads to a greater resonance, allowing it to absorb near-infrared light, which can readily penetrate tissue; 2) it has anti-corrosiveness and good biocompatibility, which makes it suitable for biomedical applications; 3) it shows a reduced net density and large surface area, allowing the possibility of nanocarriers for drug delivery. In this review, we present information on the classification, characteristics, and synthetic methods of hollow gold nanostructures; discuss the recent advances in hollow gold nanostructures in biomedical applications, including biosensing, bioimaging, photothermal therapy, and drug delivery; and report on the existing challenges and prospects for hollow gold nanostructures.

Research in biosensing currently occupies an important role among biomolecular detection techniques, especially with respect to medical diagnoses. Is this sense, the development of biosensors based on the localized surface plasmon resonance (an optical transducer) or electrochemical transductions have been highlighted. However, optical and electrochemical detection working together enable more versatile detections in biosensing. Thus, we propose a dual sensor, which incorporates these two mechanisms on the same platform. The sensor shared the same transducer that was based on a glass-indium thin oxide (ITO) surface covered with gold nanoparticles. The transducer was prepared by the immobilization of gold nanoparticles on (3-aminopropyl)triethoxysilane-activated glass-ITO. The substrate ability to respond to physical surface variations was assessed. For this, measurements of the gold nanoparticles band redshift (plasmonic transduction) and charge transfer resistance from impedance spectra (electrochemical transduction) were performed. The platform was able to detect streptavidin immobilized on the surface by both mechanisms demonstrating its applicability as a device for biodetection in dual detection mode.

To overcome low surface coverage and aggregation of particles, which usually restricts the sensitivity and resolution of conventional localized surface plasmon resonance (LSPR) fiber-optic sensors, we propose a simple self-assembled templating technique that uses a nanometer thickness block copolymer (BCP) layer of poly(styrene-b-4-vinylpyridine) to form a 33 nm gold nanoparticle (AuNP) monolayer with high uniformity and density for LSPR sensing. The LSPR resonance wavelength for this PS-b-P4VP templated methodology is 592 nm and its refractive index sensitivity is up to 386.36 nm/RIU, both of which are significantly improved compared to those of conventional LSPR techniques. Calibrated by a layer-by-layer polyelectrolyte deposition procedure, the decay length of this LSPR sensor is calculated to be 78 nm, which is lower than other traditional self-assembled LSPR sensors. Furthermore, hybridization between target ssDNA, which is linked with capture ssDNA on the LSPR biosensor and DNA–AuNP conjugates, leads to a low detection limit of 67 pM. These enhanced performances are significant and valuable for high-sensitivity and cost-effective LSPR biosensing applications.

Nonlinear interactions between light and matter give rise to a wide range of applications for both fundamental and applied research. Herein, near‐infrared switching of the optical response based on embedded Ag nanoparticles and laser‐written optical waveguides within yttrium vanadate (YVO4) crystal matrix is demonstrated. Using broadband transient absorption spectroscopy with a combination of femtosecond Z‐scan spectroscopy, the plasmon‐enhanced features of the third‐order optical nonlinearity in Ag:YVO4 nanocomposite at the near‐infrared band are elucidated. Meanwhile, an optical‐lattice‐like microscale waveguide is fabricated with well‐preserved photoluminescence properties by femtosecond laser writing. Taking advantage of the ultrafast on–off switching behavior of Ag:YVO4 saturable absorber, a Q‐switched pulsed laser operation in the waveguide platform, delivering 1 μm light pulses with high peak power of 298 mW, is demonstrated. This work indicates a possible path for the development of chip‐scale ultrafast photonic devices.

Metallic nanoparticle ensemble, with narrow inter-particle distance, is a useful element for diverse optical devices due to highly enhanced electric field intensity at the gap. Self-assembly of block copolymer (BCP) can provide the versatile solution to fabricate precise nanostructures, but this methodology has the intrinsic limitation to realize optically coupled metallic multimer geometry with narrow inter-particle distance. This is because BCP-based nanotemplate possesses a minimum size limit for interparticle distance imposed by its thermodynamic restriction. Herein, we investigate the facile formation of metallic multimer with scalability and area-selectivity through the collapse of self-assembled BCP nanopattern. The capillary-force-induced collapse phenomenon enables a spatial transformation of lateral regular ordering in metallic nanoparticle array and enhances electric field intensity. The fabrication of this metallic nanoparticle ensemble from BCP lithography is successfully utilized for surface enhanced Raman scattering (SERS). The enhancement factor of metal nanoparticle multimer is calculated as ~6.74 &times, 105 at 1000 cm&minus, 1, 2.04 &times, 106 at 1022 cm&minus, 1, and 6.11 &times, 106 at 1580 cm&minus, 1, respectively.

Surface plasmon resonance (SPR) and localized surface plasmon resonance (LSPR) are among the most common and powerful label-free refractive index-based biosensing techniques available nowadays. Focusing on LSPR sensors, their performance is highly dependent on the size, shape, and nature of the nanomaterial employed. Indeed, the tailoring of those parameters allows the development of LSPR sensors with a tunable wavelength range between the ultra-violet (UV) and near infra-red (NIR). Furthermore, dealing with LSPR along optical fiber technology, with their low attenuation coefficients at NIR, allow for the possibility to create ultra-sensitive and long-range sensing networks to be deployed in a variety of both biological and chemical sensors. This work provides a detailed review of the key science underpinning such systems as well as recent progress in the development of several LSPR-based biosensors in the NIR wavelengths, including an overview of the LSPR phenomena along recent developments in the field of nanomaterials and nanostructure development towards NIR sensing. The review ends with a consideration of key advances in terms of nanostructure characteristics for LSPR sensing and prospects for future research and advances in this field. Fundação para a Ciência e a Tecnologia | Ref. UIDB / 50014/2020 Fundação para a Ciência e a Tecnologia | Ref. POCI-01-0145-FEDER-031220 Fundação para a Ciência e a Tecnologia | Ref. FCT SFRH / BD / 146784/2019 Fundação para a Ciência e a Tecnologia | Ref. FCT CEECIND / 00471/2017 Ministerio de Ciencia e Innovación (España) | Ref. PID2019-108954R

We report the development of a real-time localized surface plasmon resonance (LSPR) biosensing strategy to detect three-dimensional morphological changes in a supported lipid bilayer (SLB) on a plasmonic substrate. The sensing concept advances on past efforts to detect subtle conformational changes in adsorbed biomacromolecules by demonstrating the capability to track large-scale, complex adsorbate shape changes and to classify different types of shape changes based on specific, multi-step measurement signatures. To validate this concept, we tested the addition of antimicrobial fatty acids, monoglycerides, and surfactants in micellar form to the SLB platform, which triggered specific three-dimensional membrane morphological changes such as tubule or bud formation along with solubilization. Experimentally, the different remodeling events were detected by distinct measurement signatures related to the shape and size of lipid protrusions that formed and evolved over time, which agreed well with a newly developed theoretical model. Our conceptual approach and formalism are applicable to various biosensing techniques, including not only LSPR but also surface plasmon resonance (SPR) and total internal reflection fluorescence (TIRF) microscopy. These sensing capabilities are advantageous for evaluating the mechanisms of antimicrobial drug candidates and other membrane-active compounds, and the measurement strategy is extendable to a wide range of biomimetic lipid compositions. This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korean government (MSIT) (No. 2020R1C1C1004385), and by the Korea Research Fellowship Program through the National Research Foundation of Korea (NRF) funded by the Ministry of Science and ICT (2019H1D3A1A01070318).

The localized surface plasmon resonance (LSPR) excitation in plasmonic nanoparticles (NPs) in the visible and near-infrared ranges is currently at the forefront of improving photocatalytic performances via plasmonic photocatalysis. One bottleneck of this field is that the NPs that often display the best optical properties in the visible and near-infrared ranges are based on expensive noble metals such as silver (Ag) and gold (Au). While earth-abundant plasmonic materials have been proposed together with catalytic metals in antenna-reactor systems, their performances remain limited by their optical properties. Importantly, the synthesis of plasmonic photocatalysts remains challenging in terms of scalability while often requiring several steps, high temperatures, and special conditions. Herein, we address these challenges by developing a one-pot, gram-scale, room-temperature synthesis of earth-abundant plasmonic photocatalysts while improving their activities beyond what has been dictated by the LSPR excitation of the plasmonic component. We describe the mechanochemical synthesis of earth-abundant plasmonic photocatalysts by using MoO3 (antenna) and Au (reactor) NPs as a proof-of-concept example and demonstrate that the dual plasmonic excitation of antenna and reactor sites enables the tuning of plasmonic photocatalytic performances toward the reductive coupling of nitrobenzene to azobenzene as a model reaction. In addition to providing a pathway to the facile and gramscale synthesis of plasmonic photocatalysts, the results reported herein may open pathways to improved activities in plasmonic catalysis.

A simple and cost-effective method is proposed herein for a plasmonic nanoantenna array (PNAA) for the fabrication of metal-enhanced fluorescence (MEF) substrates in which fluorophores interact with the enhanced electromagnetic field generated by a localized surface plasmon to provide a higher fluorescence signal. The PNAA is fabricated by the deposition of a silver (Ag) layer on an ultraviolet (UV) nanoimprinted nanodot array with a pitch of 400 nm, diameter of 200 nm, and height of 100 nm. During deposition, raised Ag nanodisks and a lower Ag layer are, respectively, formed on the top and bottom of the imprinted nanodot array, and the gap between these Ag layers acts as a plasmonic nanoantenna. Since the thickness of the gap within the PNAA is influenced by the thickness of Ag deposition, the effects of the latter upon the geometrical properties of the fabricated PNAA are examined, and the electromagnetic field intensity distributions of PNAAs with various Ag thicknesses are simulated. Finally, the fluorescence enhancement factor (FEF) of the fabricated PNAA MEF substrate is measured using spotted Cy5-conjugated streptavidin to indicate a maximum enhancement factor of ~22&times, for the PNAA with an Ag layer thickness of 75 nm. The experimental results are shown to match the simulated results.

Deterministic positioning and assembly of colloidal nanoparticles (NPs) onto substrates is a core requirement and a promising alternative to top down lithography to create functional nanostructures and nanodevices with intriguing optical, electrical, and catalytic features. Capillary-assisted particle assembly (CAPA) has emerged as an attractive technique to this end, as it allows controlled and selective assembly of a wide variety of NPs onto predefined topographical templates using capillary forces. One critical issue with CAPA, however, lies in its final printing step, where high printing yields are possible only with the use of an adhesive polymer film. To address this problem, we have developed a template dissolution interfacial patterning (TDIP) technique to assemble and print single colloidal AuNP arrays onto various dielectric and conductive substrates in the absence of any adhesion layer, with printing yields higher than 98%. The TDIP approach grants direct access to the interface between the AuNP and the target surface, enabling the use of colloidal AuNPs as building blocks for practical applications. The versatile applicability of TDIP is demonstrated by the creation of direct electrical junctions for electro- and photoelectrochemistry and nanoparticle-on-mirror geometries for single particle molecular sensing.

We report on genosensors to detect an ssDNA sequence from the SARS-CoV-2 genome, which mimics the GU280 gp10 gene (coding the viral nucleocapsid phosphoprotein), using four distinct principles of detection and treating the data with information visualization and machine learning techniques. Genosensors were fabricated on either gold (Au) interdigitated electrodes for electrical and electrochemical measurements or on Au nanoparticles on a glass slide for optical measurements. They contained a matrix of 11-mercaptoundecanoic acid (11-MUA) self-assembled monolayer (SAM) onto which a layer of capture probe (cpDNA) sequence was immobilized. Detection was performed using electrical and electrochemical impedance spectroscopies and localized surface plasmon resonance (LSPR). The highest sensitivity was reached with impedance spectroscopy, including using a low-cost (US$ 100) homemade impedance analyzer. Complementary ssDNA sequences were detected with a detection limit of 0.5 aM (0.3 copy per µL). This performance may be attributed to the high sensitivity of the electrical impedance technique combined with an appropriate arrangement of the sequences on the electrodes and hybridization between the complementary sequences, as inferred from polarization-modulated infrared reflection absorption spectroscopy (PM-IRRAS). The selectivity of the genosensor was confirmed by plotting the impedance spectroscopy data with a multidimensional projection technique (interactive document mapping, IDMAP), where a clear separation was observed among the samples of the complementary DNA sequence at various concentrations and from buffer samples containing a non-complementary sequence and other DNA biomarkers. The diagnosis of SARS-CoV-2 mimicking sequences was also achieved with machine learning techniques applied to scanning electron microscope images taken from genosensors exposed to distinct concentrations of the complementary ssDNA sequences. In summary, the genosensors proposed here are promising for detecting SARS-CoV-2 genetic material (RNA) in biological fluids in point-of-care settings., The authors are thankful to CAPES (88887.510657/2020-00 and 88887.364257/2019-00), São Paulo Research Foundation (FAPESP) (2013/14262, 2016/01919-6, 2018/18953-8, 2018/19750-3, 2018/22214-6, 2019/00101-8, 2019/13514-9, 2016/23763-8, 2019/07811-0, 2020/02938-0), INEO, INCTBio grants (FAPESP 2014/50867-3) and CNPq (423952/2018-8, 465389/2014-7, and 401256/2020-0) for the financial support. The authors are grateful to Angelo Luiz Gobbi and Maria Helena de Oliveira Piazzetta (LMF/LNNano/CNPEM) for producing the Au electrodes.

Monolayer MoS2 has attracted tremendous interest, in recent years, due to its novel physical properties and applications in optoelectronic and photonic devices. However, the nature of the atomic-thin thickness of monolayer MoS2 limits its optical absorption and emission, thereby hindering its optoelectronic applications. Hybridizing MoS2 by plasmonic nanostructures is a critical route to enhance its photoluminescence. In this work, the hybrid nanostructure has been proposed by transferring the monolayer MoS2 onto the surface of 10-nm-wide gold nanogap arrays fabricated using the shadow deposition method. By taking advantage of the localized surface plasmon resonance arising in the nanogaps, a photoluminescence enhancement of ~20-fold was achieved through adjusting the length of nanogaps. Our results demonstrate the feasibility of a giant photoluminescence enhancement for this hybrid of MoS2/10-nm nanogap arrays, promising its further applications in photodetectors, sensors, and emitters.

International audience; Direct methanol oxidation is expected to play a central role in low-polluting future power sources. However, the sluggish and complex electro-oxidation of methanol is one of the limiting factors for any practical application. To solve this issue, the use of plasmonic is considered as a promising way to accelerate the methanol oxidation reaction. In this study, we report on a novel approach for achieving enhanced methanol oxidation currents. Perforated gold thin film anodes were decorated with Pt/Ru via electrochemical deposition and investigated for their ability for plasmon-enhanced electrocatalytic methanol oxidation in alkaline media. The novel methanol oxidation anode (AuNHs/PtRu), combining the strong light absorption properties of a gold nanoholes array-based electrode (AuNHs) with surface-anchored bimetallic Pt/Ru nanostructures, known for their high activity toward methanol oxidation, proved to be highly efficient in converting methanol via the hot holes generated in the plasmonic electrode. Without light illumination, AuNHs/PtRu displayed a maximal current density of 13.7 mA/cm2 at -0.11 V vs Ag/AgCl. Enhancement to 17.2 mA/cm2 was achieved under 980 nm laser light illumination at a power density of 2 W/cm2. The thermal effect was negligible in this system, underlining a dominant plasmon process. Fast generation and injection of charge carriers were also evidenced by the abrupt change in the current density upon laser irradiation. The good stability of the interface over several cycles makes this system interesting for methanol electro-oxidation.

Scanning transmission electron microscopy (STEM) combined with electron energy loss spectroscopy (EELS) has become a standard technique to map localized surface plasmon resonances with a nanometer spatial and a sufficient energy resolution over the last 15 years. However, no experimental work discussing the influence of experimental conditions during the measurement has been published up to now. We present an experimental study of the influence of the primary beam energy and the collection semi-angle on the plasmon resonances measurement by STEM-EELS. To explore the influence of these two experimental parameters we study a series of gold rods and gold bow-tie and diabolo antennas. We discuss the impact on experimental characteristics which are important for successful detection of the plasmon peak in EELS, namely: the intensity of plasmonic signal, the signal to background ratio, and the signal to zero-loss peak ratio. We found that the primary beam energy should be high enough to suppress the scattering in the sample and at the same time should be low enough to avoid the appearance of relativistic effects. Consequently, the best results are obtained using a medium primary beam energy, in our case 120 keV, and an arbitrary collection semi-angle, as it is not a critical parameter at this primary beam energy. Our instructive overview will help microscopists in the field of plasmonics to arrange their experiments.

Metal-enhanced fluorescence (MEF) is a unique phenomenon of surface plasmons, where light interacts with the metallic nanostructures and produces electromagnetic fields to enhance the sensitivity of fluorescence-based detection. In particular, this enhancement in sensing capacity is of importance to many research areas, including medical diagnostics, forensic science, and biotechnology. The article covers the basic mechanism of MEF and recent developments in plasmonic nanostructures fabrication for efficient fluorescence signal enhancement that are critically reviewed. The implications of current fluorescence-based technologies for biosensors are summarized, which are in practice to detect different analytes relevant to food control, medical diagnostics, and forensic science. Furthermore, characteristics of existing fabrication methods have been compared on the basis of their resolution, design flexibility, and throughput. The future projections emphasize exploring the potential of non-conventional materials and hybrid fabrication techniques to further enhance the sensitivity of MEF-based biosensors.